CN107629020A - A kind of (6H) ketone compounds of 1,2,4 oxadiazines of 4H 5 and its synthetic method - Google Patents
A kind of (6H) ketone compounds of 1,2,4 oxadiazines of 4H 5 and its synthetic method Download PDFInfo
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Abstract
The invention discloses a kind of (6H) ketone derivatives of 1,2,4 oxadiazines of 4H 5 and its synthetic method, belong to compound synthesis technical field.In equipped with container of the substitution α halogen acid amides with substituting chlorination oxime compound, add solvent and alkali, stirred under 25 DEG C 100 DEG C of reaction temperature, reaction is washed after terminating with water or saturated salt solution, is then extracted with organic solvent, dry, it is evaporated under reduced pressure concentration and removes solvent, crude product produces target product 4H 1 through pillar layer separation, 2,4 oxadiazine 5 (6H) ketone compounds.This method has the advantages that no transition-metal catalyst, raw material cheap and easy to get, reaction substrate wide adaptability, reaction condition is gentle, regioselective is good, yield is high, green, has good prospects for commercial application.
Description
Technical field
The invention belongs to technical field of organic synthesis, is related to a kind of 4H-1,2,4- oxadiazine -5 (6H) -one class compounds
And its synthetic method.
Background technology
In current world pesticide patent, the compound that probably has 90% is heterocyclic compound, heterocyclic compound into
For the trend of novel pesticide development.Oxadiazine insecticides be using sodium-ion channel as major target, to neuron nAchRs and
GABA acceptors etc. have the novel green insecticide of multiple action, have the features such as ultra high efficiency, high selectivity, low-residual, extensively
It is general to be used for agricultural chemicals, medicine and other fields.
Oxadiazine class is the structure of numerous research workers' concern, is the key heterocycle of many agricultural chemicals, medicine intermediate
Construction unit, it is one of study hotspot of research worker.Nearest Hongjun ZHU research group reports NIS and BF3Et2O and promoted
1,3,5- oxadiazine -2- the ketone derivatives of the cyclisation structure iodine substitution of the ynamine and acetonitrile of the Boc protections entered；Zhao's literature research is small
The cyclisation that group reports the alkynyl amide and nitrile that promote using iodine builds 1,3,5- oxadiazine -2- ketone derivatives；
After Loiseleur groups are first with diethylaminosulfurtrifluoride (DAST) catalytic cyclization α, α-two substitution-α-acyl amino ketone, then
Carry out oxyammonia and hydrolyze get Dao oxadiazine ketones derivant；Multi-step conversion passes through using 2- hydroxy-iso-butyronitriles in Humphrey research groups
Ke get are Dao oxadiazine ketone construction unit etc..(bibliography： Org.Lett.2015,17,2510；J.Org.Chem.2012,77,
9871； Chin.J.Org.Chem.2015,35,2108；Org.Lett.13,192；Org. Process Res.Dev.2011,
15,73。)
But unmanned report utilizes alpha-halogen acid amides and substitution chlorination oxime compound dipole dipole-diople interaction Gou Jian Evil so far
Thiadiazinthion construction unit, therefore the synthesis that the present invention will provide a kind of mild condition, simple to operate, raw material is cheap, green
The method of 1,2,4- oxadiazines -5 (6H) -one.
The content of the invention
The invention aims to provide a kind of 4H-1,2,4- oxadiazines -5 (6H) -one class compound and its synthesis side
Method, this method have that reaction condition is gentle, simple to operate, raw material is cheap, the advantage such as green.
In order to realize the purpose of the present invention, the technical scheme of use is：
A kind of 4H-1,2,4- oxadiazine -5 (6H) -one class compounds, it is characterised in that its structural formula is as follows：
Wherein R1 be C1~C5 alkyl, methoxyl group, the tert-butyl group, pentamethylene base, thiacyclohexane base, phenyl, 4- aminomethyl phenyls,
4- methoxyphenyls, 4- fluorophenyls, 4- chlorphenyls, 4- bromophenyls, 4- cyanophenyls, 4- aminocarbonyl phenyls, 2- aminomethyl phenyls, 2- first
Phenyl, 2- fluorophenyls, 2- chlorphenyls, 2- bromophenyls, 2- cyanophenyls, 3- aminomethyl phenyls, 3- methoxyphenyls, 3- fluorobenzene
Any one in base, 3- chlorphenyls, 3- bromophenyls or 3- cyanophenyls etc.；
R2 is hydrogen, C1~C5 alkyl, methoxyl group, the tert-butyl group, pentamethylene base, thiacyclohexane base, phenyl, rubigan, right
Bromophenyl, 3- fluorophenyls, any one in p-methylphenyl or 3- methoxyphenyls etc.；
R3 be hydrogen, C1~C5 alkyl, benzyloxy, to benzyl chloride epoxide, to bromo-benzyloxy, 3- fluorine benzyloxies, to methyl benzyl
Any one in epoxide or 3- methoxybenzyl epoxides etc.；
X is any one in chlorine, bromine or iodine.
A kind of 4H-1, the synthetic method of 2,4- oxadiazine -5 (6H) -one class compounds, it is characterised in that including step：
In container equipped with substitution alpha-halogen acid amides with substituting chlorination oxime compound, solvent and alkali are added, in 25 DEG C -100 DEG C of reaction
At a temperature of stir, reaction terminate after wash with water or saturated salt solution, then extracted with organic solvent, drying, vacuum distillation it is dense
Contracting removes solvent, and crude product produces target product 4H-1,2,4- oxadiazine -5 (6H) -one class compounds through pillar layer separation.
The organic solvent is selected from trifluoro methanol, trifluoroethanol, hexafluoroisopropanol, N, N- dimethylformamides, diformazan
In sulfoxide, acetonitrile, 1,4- dioxane, tetrahydrofuran, toluene, dichloromethane, 1,2- dimethylbenzene or 1,2- dichloroethanes etc.
It is one or more.
The alkali be for NaOH, KOH, K2CO3, Na2CO3, Cs2CO3, C2H5OK, C2H5ONa, NaOAc, KOAc,
One or more in TEA, pyridine etc..
The dosage of the alkali is the 200-400% of the substitution chlorination oxime compound.
Described alkali, substitution alpha-halogen amide compound and the mol ratio between chlorination oxime is substituted to be [2.0~4.0]：1：
[1.0~2.0].
Described α halogen acid amides are selected from the bromo- 2- methyl propanamides of N- benzyloxies -2-, N- benzyloxy -2- chloro-2-methyls
The iodo- 2- methyl propanamides of propionamide, N- benzyloxies -2-, the bromo- propionamides of N- benzyloxies -2-, the chloro- propionamides of N- benzyloxies -2-,
The iodo- propionamides of N- benzyloxies -2-, N- benzyloxy -1- bromine cyclohexyl -1- formamides, N- benzyloxy -1- chlorine cyclohexyl -1- first
Acid amides, N- benzyloxy -1- iodine cyclohexyl -1- formamides, N- benzyloxy -1- chlorine cyclopenta -1- formamides, N- benzyloxy -1- bromines
Any one in cyclopenta -1- formamides or N- benzyloxy -1- iodine cyclopenta -1- formamides.
Described substitution chlorination oxime compound is alkyl chlorination oxime, methoxyl group chlorination oxime, tertiary butyl chloride selected from C1~C5
Change oxime, pentamethylene base chlorination oxime, thiacyclohexane base chlorination oxime, tetraphenylphosphonium chloride oxime, 4- methylbenzene chlorinations oxime, 4- ethylo benzene chlorinations oxime,
4- methoxybenzene chlorinations oxime, 4- tert-butyl benzene chlorinations oxime, 4- fluorobenzene chlorinations oxime, 4- bromobenzene chlorinations oxime, 4- nitrobenzene chlorinations oxime, 4-
Itrile group benzene chlorination oxime, 4- acetylbenzene chlorinations oxime, 3- methylbenzene chlorinations oxime, 3- ethylo benzene chlorinations oxime, 3- methoxybenzene chlorinations oxime,
3- tert-butyl benzene chlorinations oxime, 3- fluorobenzene chlorinations oxime, 3- bromobenzene chlorinations oxime, 3- nitrobenzene chlorinations oxime, 3- itrile group benzene chlorinations oxime, 3-
Acetylbenzene chlorination oxime, 2- thiophene chlorinations oxime, 2- furans chlorinations oxime, 2- pyrroles's chlorination oxime, 2- methylbenzene chlorinations oxime, 2- ethylo benzenes
Chlorination oxime, 2- methoxybenzene chlorinations oxime, 2- tert-butyl benzene chlorinations oxime, 2- fluorobenzene chlorinations oxime, 2- bromobenzene chlorinations oxime, 2- nitrobenzene chlorine
Change any one in oxime, 2- itrile group benzene chlorinations oxime, 2- acetylbenzene chlorination oximes etc..
The device have the advantages that：
It is provided by the present invention in the basic conditions, synthesize pyrrolones with raw material cheap and easy to get in gentle environment
Class compound, the selectivity and yield of product are all very high, green, have good prospects for commercial application.
Brief description of the drawings
Fig. 1 is the reaction equation of target product 4H-1,2,4- oxadiazines -5 (6H) -one class compound
The 1H NMR figures of (the 6H)-ketone of Fig. 2 4- (benzyloxy) -6- methyl -3- phenyl -4H-1,2,4- oxadiazines -5
The 13C NMR figures of (the 6H)-ketone of Fig. 3 4- (benzyloxy) -6- methyl -3- phenyl -4H-1,2,4- oxadiazines -5
Embodiment
It is the specific embodiment of the present invention and with reference to accompanying drawing below, technical scheme is further described,
But the present invention is not limited to these embodiments.
The synthesis of 4H-1,2,4- oxadiazines -5 (6H) -one compound：
As shown in figure 1,4H-1 provided by the invention, the synthesis of 2,4- oxadiazine -5 (6H) -one class Compound Compounds (I)
Step is：The alpha-halogen acid amides (II) of 0.1mmol substitutions is added in reaction vessel (such as：The bromo- 2- methyl-props of N- benzyloxies -2-
Acid amides etc.), substitution chlorination oxime (III) 0.1~0.2mmol, 200~400mol% of alkali (are based on compound (II)), then add 1-
2ml solvents are (such as：Acetonitrile), 25-100 DEG C of reaction, after reaction terminates, washed with water or saturated salt solution, then use organic solvent
Extraction, dry, be evaporated under reduced pressure concentration and remove solvent, crude product produces target product through pillar layer separation.
Embodiment 1
The synthesis of (the 6H)-ketone of 4- (benzyloxy) -6,6- dimethyl -3- phenyl -4H-1,2,4- oxadiazines -5
2.0mmol Na2CO3 is added in reaction vessel, 0.12mmol tetraphenylphosphonium chloride oximes, then adds 1ml acetonitriles,
0.12mmol alpha-halogens acid amides (the bromo- 2- methyl propanamides of N- (benzyloxy) -2-), 50 DEG C of reactions, after reaction terminates, use is water-soluble
Liquid washs, and is then extracted with organic solvent, dries, and is evaporated under reduced pressure concentration and removes solvent, crude product produces mesh through pillar layer separation
Mark product, yield 86%.
Embodiment 2
The synthesis of (6H) -one of 4- (benzyloxy) -6,6- dimethyl -3- p-methylphenyl -4H-1,2,4- oxadiazines -5
2mmol K2CO3 is added in reaction vessel, 0.12mmol 4- aminomethyl phenyl chlorination oximes, then adds 1ml second
Nitrile, 0.1mmol alpha-halogens acid amides (the bromo- 2- methyl propanamides of N- (benzyloxy) -2-), 50 DEG C of reactions, after reaction terminates, use is water-soluble
Liquid washs, and is then extracted with organic solvent, dries, and is evaporated under reduced pressure concentration and removes solvent, crude product produces mesh through pillar layer separation
Mark product, yield 75%.
Embodiment 3
The synthesis of (6H) -one of 4- (benzyloxy) -6,6- dimethyl -3- p-fluorophenyl -4H-1,2,4- oxadiazines -5
2mmol NaOH is added in reaction vessel, 0.12mmol 4- fluorophenyl chlorination oximes, then adds 1ml acetonitriles,
0.12mmol alpha-halogens acid amides (the bromo- 2- methyl propanamides of N- (benzyloxy) -2-), 50 DEG C of reactions, after reaction terminates, uses the aqueous solution
Washing, is then extracted with organic solvent, is dried, and is evaporated under reduced pressure concentration and is removed solvent, crude product produces target through pillar layer separation
Product, yield 55%.
Embodiment 4
The synthesis of chlorphenyl -4H-1,2,4- oxadiazines -5 (6H) -one between 4- (benzyloxy) -6,6- dimethyl -3-
2mmol Et3N is added in reaction vessel, 0.12mmol m-chloro tetraphenylphosphonium chloride oximes, then adds 1ml THF,
0.1mmol alpha-halogens acid amides (the bromo- 2- methyl propanamides of N- (benzyloxy) -2-), 50 DEG C of reactions, after reaction terminates, uses the aqueous solution
Washing, is then extracted with organic solvent, is dried, and is evaporated under reduced pressure concentration and is removed solvent, crude product produces target through pillar layer separation
Product, yield 62%.
Embodiment 5
The synthesis of 4- (benzyloxy) -6,6- dimethyl -3- (thiophene -2- bases) -4H-1,2,4- oxadiazines -5 (6H) -one
2mmol Na2CO3 is added in reaction vessel, 0.12mmol 2- thiophene chlorination oximes, then adds 1ml acetonitriles,
0.12mmol alpha-halogens acid amides (the bromo- 2- methyl propanamides of N- (benzyloxy) -2-), 50 DEG C of reactions, after reaction terminates, use is water-soluble
Liquid washs, and is then extracted with organic solvent, dries, and is evaporated under reduced pressure concentration and removes solvent, crude product produces mesh through pillar layer separation
Mark product, yield 81%.
Embodiment 6
The synthesis of (6H) -one of 4- (benzyloxy) -6,6- dimethyl -3- Chloro-O-Phenyl -4H-1,2,4- oxadiazines -5
Add 2mmol Na2CO3 in reaction vessel, 0.1mmol Chloro-O-Phenyl chlorination oximes, then add 1ml Isosorbide-5-Nitraes-
Dioxane, 0.12mmol alpha-halogens acid amides (the bromo- 2- methyl propanamides of N- (benzyloxy) -2-), 50 DEG C of reactions, reaction terminate
Afterwards, washed with the aqueous solution, then extracted with organic solvent, dried, be evaporated under reduced pressure concentration and remove solvent, crude product is through column chromatography point
From producing target product, yield 70%.
Embodiment 7
The synthesis of (the 6H)-ketone of 4- (benzyloxy) -6,6- dimethyl -3- propyl group -4H-1,2,4- oxadiazines -5
In reaction vessel add 2mmol CS2CO3,0.12mmol heptyne, then add 1ml acetonitriles, 0.1mmol α-
Halogen acid amide (the bromo- 2- methyl propanamides of N- (benzyloxy) -2-), 50 DEG C of reactions, after reaction terminates, is washed, then with the aqueous solution
Extracted, dried with organic solvent, be evaporated under reduced pressure concentration and remove solvent, crude product produces target product, yield through pillar layer separation
52%.
Embodiment 8
The synthesis of (6H) -one of 4- (benzyloxy) -6- methyl -3- phenyl -4H-1,2,4- oxadiazines -5
2.0mmol Na2CO3 is added in reaction vessel, 0.12mmol tetraphenylphosphonium chloride oximes, then adds 1ml acetonitriles,
0.12mmol alpha-halogens acid amides (the bromo- propionamides of N- (benzyloxy) -2-), 50 DEG C of reactions, after reaction terminates, is washed with the aqueous solution,
Then being extracted, dried with organic solvent, be evaporated under reduced pressure concentration and remove solvent, crude product produces target product through pillar layer separation,
Yield 89%.
Embodiment 9
The synthesis of (the 6H)-ketone of 4- (benzyloxy) -6- methyl -3- p-methylphenyl -4H-1,2,4- oxadiazines -5
2mmol K2CO3 is added in reaction vessel, 0.12mmol 4- aminomethyl phenyl chlorination oximes, then adds 1ml second
Nitrile, 0.1mmol alpha-halogens acid amides (the bromo- propionamides of N- (benzyloxy) -2-), 50 DEG C of reactions, after reaction terminates, washed with the aqueous solution
Wash, then extracted with organic solvent, dried, be evaporated under reduced pressure concentration and remove solvent, crude product produces target production through pillar layer separation
Thing, yield 80%.
Embodiment 10
The synthesis of (the 6H)-ketone of 4- (benzyloxy) -6- methyl -3- p-fluorophenyl -4H-1,2,4- oxadiazines -5
2mmol NaOH is added in reaction vessel, 0.12mmol 4- fluorophenyl chlorination oximes, then adds 1ml acetonitriles,
0.12mmol alpha-halogens acid amides (the bromo- propionamides of N- (benzyloxy) -2-), 50 DEG C of reactions, after reaction terminates, is washed with the aqueous solution,
Then being extracted, dried with organic solvent, be evaporated under reduced pressure concentration and remove solvent, crude product produces target product through pillar layer separation,
Yield 50%.
Embodiment 11
The synthesis of (the 6H)-ketone of chlorphenyl -4H-1,2,4- oxadiazines -5 between 4- (benzyloxy) -6- methyl -3-
2mmol Et3N is added in reaction vessel, 0.12mmol m-chloro tetraphenylphosphonium chloride oximes, then adds 1ml THF,
0.1mmol alpha-halogens acid amides (the bromo- propionamides of N- (benzyloxy) -2-), 50 DEG C of reactions, after reaction terminates, is washed with the aqueous solution,
Then being extracted, dried with organic solvent, be evaporated under reduced pressure concentration and remove solvent, crude product produces target product through pillar layer separation,
Yield 72%.
Embodiment 12
The synthesis of 4- (benzyloxy) -6- methyl -3- (thiophene -2- bases) -4H-1,2,4- oxadiazines -5 (6H) -one
2mmol Na2CO3 is added in reaction vessel, 0.12mmol 2- thiophene chlorination oximes, then adds 1ml acetonitriles,
0.12mmol alpha-halogens acid amides (the bromo- propionamides of N- (benzyloxy) -2-), 50 DEG C of reactions, after reaction terminates, is washed with the aqueous solution,
Then being extracted, dried with organic solvent, be evaporated under reduced pressure concentration and remove solvent, crude product produces target product through pillar layer separation,
Yield 93%.
Embodiment 13
The synthesis of (the 6H)-ketone of 4- (benzyloxy) -6- methyl -3- Chloro-O-Phenyl -4H-1,2,4- oxadiazines -5
Add 2mmol Na2CO3 in reaction vessel, 0.1mmol Chloro-O-Phenyl chlorination oximes, then add 1ml Isosorbide-5-Nitraes-
Dioxane, 0.12mmol alpha-halogens acid amides (the bromo- propionamides of N- (benzyloxy) -2-), 50 DEG C of reactions, after reaction terminates, use water
Solution washs, and is then extracted with organic solvent, dries, and is evaporated under reduced pressure concentration and removes solvent, crude product produces through pillar layer separation
Target product, yield 65%.
Embodiment 14
The synthesis of (6H) -one of 4- (benzyloxy) -6- methyl -3- propyl group -4H-1,2,4- oxadiazines -5
In reaction vessel add 2mmol CS2CO3,0.12mmol heptyne, then add 1ml acetonitriles, 0.1mmol α-
Halogen acid amide (the bromo- propionamides of N- (benzyloxy) -2-), 50 DEG C of reactions, after reaction terminates, is washed, then with organic with the aqueous solution
Solvent extraction, dry, be evaporated under reduced pressure concentration and remove solvent, crude product produces target product, yield 61% through pillar layer separation.
Nuclear magnetic resonant collection of illustrative plates as shown in Figures 2 and 3 can be seen that it is provided by the present invention in the basic conditions, in temperature
Pyrrolidone compound is synthesized with raw material cheap and easy to get in the environment of sum, the selectivity and yield of product are all very high, green
Environmental protection, there is good prospects for commercial application
Specific embodiment described herein is only to spirit explanation for example of the invention.Technology belonging to the present invention is led
The technical staff in domain can be made various modifications or supplement to described specific embodiment or be replaced using similar mode
Generation, but without departing from the spiritual of the present invention or surmount scope defined in appended claims.
Claims (8)
1. a kind of 4H-1,2,4- oxadiazine -5 (6H) -one class compounds, it is characterised in that its structural formula is as follows：
Wherein R1 is C1~C5 alkyl, methoxyl group, the tert-butyl group, pentamethylene base, thiacyclohexane base, phenyl, 4- aminomethyl phenyls, 4- first
Phenyl, 4- fluorophenyls, 4- chlorphenyls, 4- bromophenyls, 4- cyanophenyls, 4- aminocarbonyl phenyls, 2- aminomethyl phenyls, 2- methoxyl groups
Phenyl, 2- fluorophenyls, 2- chlorphenyls, 2- bromophenyls, 2- cyanophenyls, 3- aminomethyl phenyls, 3- methoxyphenyls, 3- fluorophenyls,
Any one in 3- chlorphenyls, 3- bromophenyls or 3- cyanophenyls etc.；
R2 be hydrogen, C1~C5 alkyl, methoxyl group, the tert-butyl group, pentamethylene base, thiacyclohexane base, phenyl, rubigan, to bromobenzene
Base, 3- fluorophenyls, any one in p-methylphenyl or 3- methoxyphenyls etc.；
R3 be hydrogen, C1~C5 alkyl, benzyloxy, to benzyl chloride epoxide, to bromo-benzyloxy, 3- fluorine benzyloxies, to methylbenzyloxy
Or any one in 3- methoxybenzyl epoxides etc.；
X is any one in chlorine, bromine or iodine.
2. a kind of 4H-1 according to claim 1, the synthetic method of 2,4- oxadiazine -5 (6H) -one class compounds, it is special
Sign is that this synthetic method comprises the following steps：
A, in equipped with container of the substitution alpha-halogen acid amides with substituting chlorination oxime compound, solvent and alkali are added；
B, stirred under 25 DEG C -100 DEG C of reaction temperature, reaction is washed after terminating with water or saturated salt solution；
C, and then with organic solvent extract, dry, be evaporated under reduced pressure concentration and remove solvent；
D, crude product produces target product 4H-1,2,4- oxadiazine -5 (6H) -one class compounds through pillar layer separation.
3. a kind of 4H-1 according to claim 2, the synthetic method of 2,4- oxadiazine -5 (6H) -one class compounds, it is special
Sign is that the organic solvent is sub- selected from trifluoro methanol, trifluoroethanol, hexafluoroisopropanol, DMF, diformazan
One in sulfone, acetonitrile, 1,4- dioxane, tetrahydrofuran, toluene, dichloromethane, 1,2- dimethylbenzene or 1,2- dichloroethanes etc.
Kind is a variety of.
4. a kind of 4H-1 according to claim 2, the synthetic method of 2,4- oxadiazine -5 (6H) -one class compounds, it is special
Sign is, the alkali be for NaOH, KOH, K2CO3, Na2CO3, Cs2CO3, C2H5OK, C2H5ONa, NaOAc, KOAc, TEA,
One or more in pyridine etc..
5. a kind of 4H-1 according to claim 2, the synthetic method of 2,4- oxadiazine -5 (6H) -one class compounds, it is special
Sign is that the dosage of the alkali is the 200-400% of the substitution chlorination oxime compound.
6. a kind of 4H-1 according to claim 2, the synthetic method of 2,4- oxadiazine -5 (6H) -one class compounds, it is special
Sign is that the mol ratio between described alkali, substitution alpha-halogen amide compound and substitution chlorination oxime is [2.0~4.0]：1：
[1.0~2.0].
7. a kind of 4H-1 according to claim 2, the synthetic method of 2,4- oxadiazine -5 (6H) -one class compounds, it is special
Sign is that described alpha-halogen acid amides is selected from the bromo- 2- methyl propanamides of N- benzyloxies -2-, N- benzyloxy -2- chloro-2-methyls
The iodo- 2- methyl propanamides of propionamide, N- benzyloxies -2-, the bromo- propionamides of N- benzyloxies -2-, the chloro- propionamides of N- benzyloxies -2-,
The iodo- propionamides of N- benzyloxies -2-, N- benzyloxy -1- bromine cyclohexyl -1- formamides, N- benzyloxy -1- chlorine cyclohexyl -1- formyls
Amine, N- benzyloxy -1- iodine cyclohexyl -1- formamides, N- benzyloxy -1- chlorine cyclopenta -1- formamides, N- benzyloxy -1- bromine rings
Any one in amyl group -1- formamides or N- benzyloxy -1- iodine cyclopenta -1- formamides etc..
8. a kind of 4H-1 according to claim 2, the synthetic method of 2,4- oxadiazine -5 (6H) -one class compounds, it is special
Sign is that described substitution chlorination oxime compound is the alkyl chlorination oxime selected from C1~C5, methoxyl group chlorination oxime, tert-butyl group chlorination
Oxime, pentamethylene base chlorination oxime, thiacyclohexane base chlorination oxime, tetraphenylphosphonium chloride oxime, 4- methylbenzene chlorinations oxime, 4- ethylo benzene chlorinations oxime, 4-
Methoxybenzene chlorination oxime, 4- tert-butyl benzene chlorinations oxime, 4- fluorobenzene chlorinations oxime, 4- bromobenzene chlorinations oxime, 4- nitrobenzene chlorinations oxime, 4- nitriles
Base benzene chlorination oxime, 4- acetylbenzene chlorinations oxime, 3- methylbenzene chlorinations oxime, 3- ethylo benzene chlorinations oxime, 3- methoxybenzene chlorinations oxime, 3-
Tert-butyl benzene chlorination oxime, 3- fluorobenzene chlorinations oxime, 3- bromobenzene chlorinations oxime, 3- nitrobenzene chlorinations oxime, 3- itrile group benzene chlorinations oxime, 3- acetyl
Base benzene chlorination oxime, 2- thiophene chlorinations oxime, 2- furans chlorinations oxime, 2- pyrroles's chlorination oxime, 2- methylbenzene chlorinations oxime, 2- ethylo benzene chlorinations
Oxime, 2- methoxybenzene chlorinations oxime, 2- tert-butyl benzene chlorinations oxime, 2- fluorobenzene chlorinations oxime, 2- bromobenzene chlorinations oxime, 2- nitrobenzene chlorinations
Any one in oxime, 2- itrile group benzene chlorinations oxime, 2- acetylbenzene chlorination oximes etc..
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| CN108947995A (en) * | 2018-09-17 | 2018-12-07 | 青岛科技大学 | A kind of preparation method of polysubstituted dxadiazine derivatives |
| CN109265382A (en) * | 2018-11-09 | 2019-01-25 | 湖北科技学院 | A kind of fluorine-containing thiocarbamates compound and its synthetic method |
| CN109942559A (en) * | 2019-03-08 | 2019-06-28 | 上海大学 | Furans bigeminy azole compounds and preparation method thereof |
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| CN108947995B (en) * | 2018-09-17 | 2021-03-16 | 青岛科技大学 | Preparation method of polysubstituted oxadiazine derivative |
| CN109265382A (en) * | 2018-11-09 | 2019-01-25 | 湖北科技学院 | A kind of fluorine-containing thiocarbamates compound and its synthetic method |
| CN109942559A (en) * | 2019-03-08 | 2019-06-28 | 上海大学 | Furans bigeminy azole compounds and preparation method thereof |
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